JPH1081639A - Production of pesticide-controlling fluoroolefin compound and its intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for effectively and efficiently producing pesticide- controlling fluoroolefin compound and to obtain an intermediate useful for the production of the fluoroolefin compound. SOLUTION: A compound of formula I [R is H or a 1-4C alkyl; R1 is a 1-4C alkyl, cyclopropyl, etc.; Ar is phenyl (substituted by a halogen, a 1-4C alkyl, etc.), etc.] is reacted with about 1mol equivalent bromination agent preferably at about 50-130 deg.C, in the presence of the first solvent (e.g. tetrachloroethane) to provide an intermediate of 4-aryl-1-bromo-2-fluoro-2-butene compound of formula II, and the compound of formula II is further reacted with at least about 2mol equivalent base and a boric acid of the formula (HO)2 B-Ar1 [Ar1 is a phenoxyphenyl (substituted by a halogen, a 1-4C alkyl, etc.), etc.] at about 50-130 deg.C in the presence of the second solvent (e.g. a mixture of toluene and methanol) under about 0.001-0.1mol equivalent Pd catalyst to provide the objective fluoroolefin compound of formula III in the method for producing the pesticidal fluoroolefin compound. The compound of formula III is isolated by diluting the reaction mixture by water and extracting the diluted mixture with a suitable solvent such as ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Pesticidal agents
Fluoroolefin compounds useful as WO 9
4 / 06,741 and UK Patent Application Publication No. 2,288,
No. 803. These references also describe methods for preparing fluoroolefin compounds. However, these methods produce fluoroolefin compounds in relatively low yields. Therefore, these methods are not entirely satisfactory. Also, these references do not teach how to make the intermediate compounds of the present invention.

[0002]

SUMMARY OF THE INVENTION The present invention provides a compound of formula I

[0003]

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Wherein R is hydrogen or C ₁ -C ₄ alkyl, R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ are the carbon atoms to which they are attached. Together form a cyclopropyl group; Ar
Is phenyl optionally substituted with any combination of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups. or optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C _4, in any combination of one to three haloalkoxy groups may be substituted Ar ₁ is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C 1-or 2-naphthyl;
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
Good phenoxyphenyl optionally substituted with any combination of 1 to 5 haloalkoxy group, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ ~
C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5
Any combination may biphenyl optionally substituted with the number, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5 Benzylphenyl optionally substituted with any combination of the above, or optionally halogen,
Benzoylphenyl optionally substituted with any combination of 1 to 5 C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups; And the configuration of the groups ArCRR ₁ — and —CH ₂ Ar _{1 to} the double bond is predominantly trans to produce a fluoroolefin compound having structural formula II

[0005]

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Wherein a 4-aryl-2-fluoro-2-buten-1-ol compound having Ar, R and R ₁ is as defined above is reacted with a brominating agent to form a compound of formula III

[0007]

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Wherein Ar, R and R ₁ are as described above to produce a 4-aryl-1-bromo-2-fluoro-2-butene compound having the formula: Base and boric acid having structural formula IV, boric anhydride having structural formula V or boric ester having structural formula VI

[0009]

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Wherein R ₂ is C ₁ -C ₄ alkyl, and Ar ₁ is as described above, wherein the pest controlling fluoroolefin compound having structural formula I comprises reacting And an efficient manufacturing method.

The present invention also relates to intermediate 4-aryl-1-bromo-2-fluoro-2-butene compounds of formula III.

Accordingly, it is an object of the present invention to provide an effective and efficient method for producing a pesticidal fluoroolefin compound.

Another object of the present invention is to provide an intermediate compound which is useful for producing a pesticidal fluoroolefin compound.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the following description and the appended claims.

[0015]

DETAILED DESCRIPTION OF THE INVENTION A preferred embodiment of the present invention is a compound of formula II
-Aryl-2-fluoro-2-buten-1-ol is reacted with at least about 1 molar equivalent of a brominating agent in the presence of a first solvent, preferably in a temperature range of about 50 to 130 ° C, to form a compound of formula III 4-aryl-1-bromo-2-fluoro-
2-butene is formed and the compound of formula III is converted to about 50
In the presence of a second solvent in a temperature range of
01 to 0.1, preferably about 0.005 to 0.1 molar equivalents of palladium catalyst, at least about 2 molar equivalents, preferably about 2 to 6 molar equivalents of base and boric acid of formula IV, preferably 1 molar equivalent Reacting with boric acid.

The present invention also relates to the method used in the method of the present invention.
-Aryl-1-bromo-2-fluoro-2-butene compounds. The 4-aryl-1-bromo-2-fluoro-2-butene compound has the structural formula III

[0017]

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Wherein R is hydrogen or C ₁ -C ₄ alkyl and R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ are the carbon atoms to which they are attached together with form a cyclopropyl group; Ar is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄
Phenyl optionally substituted with any combination of 1 to 3 haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups, or optionally halogen, C ₁ -C ₄
1- or 2-optionally substituted with any combination of 1 to 3 C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups.
And the group A for the double bond
The configurations of rCRR ₁ — and —CH ₂ Br are mainly trans to each other.

Examples of the above halogens include fluorine, chlorine, bromine and iodine. The terms “C ₁ -C ₄ haloalkyl” and “C ₁ -C ₄ haloalkoxy” refer to C ₁ -C ₄ alkyl groups and C ₁ -C ₄ alkoxy groups, respectively, substituted with one or more halogen atoms. Defined.

The product of the compound of formula I can be isolated by diluting the reaction mixture with water and extracting the product with a suitable extraction solvent. In the isolation step, conventional extraction solvents such as ether, ethyl acetate, toluene, methylene chloride and the like can be used.

The brominating agents suitable for the process of the present invention include bromine /
Examples include, but are not limited to, triphenylphosphine complexes, phosphorus tribromide, thionyl bromide, concentrated hydrobromic acid, and the like, and mixtures thereof. Bromine / triphenylphosphine complexes are preferred brominating agents.

First solvents suitable for use in the present invention include aromatic hydrocarbons such as toluene, benzene, xylene,
Halogenated aromatic hydrocarbons such as mesitylene and the like, chlorobenzene, fluorobenzene and the like, carboxamides such as N, N-dimethylformamide and the like, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride and the like And mixtures thereof, but is not limited thereto. Suitable first solvents include halogenated hydrocarbons, with carbon tetrachloride being more preferred.

The second solvent which can be used in the process of the present invention includes aromatic hydrocarbons such as toluene, benzene, xylene and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene, carboxylic acid amides such as N and N- dimethylformamide, glycols such as dimethoxyethane, C ₁ -C ₄ alcohols such as methanol, ethanol and the like, such as ketones such as acetone, ethers such as tetrahydrofuran, dioxane and mixtures thereof, as well as mixtures with water, It is not limited to this. Suitable second solvents include aromatic hydrocarbons and aromatic hydrocarbon / C ₁ -C ₄ alcohol mixtures, with toluene / ethanol mixtures being more preferred.

Palladium catalysts suitable for use in the present invention include palladium (0) catalysts such as bis (dibenzylideneacetone) palladium (0), tetrakis (triphenylphosphine) palladium (0), and the like. (Acetonitrile) palladium (II), bis (triphenylphosphine) palladium (II) chloride, [1,4-bis (diphenylphosphine) butane] palladium (II) dichloride, diacetate [1,1′-
Bis (diphenylphosphino) ferrocene] palladium (II), palladium (II) acetate, palladium (II) chloride
And palladium on activated carbon and mixtures thereof, but are not limited thereto. Suitable catalysts include palladium (0) catalysts, with bis (dibenzylideneacetone) palladium (0) being more preferred.

Bases suitable for use in the present invention include alkali metal carbonates such as sodium and potassium carbonate, alkaline earth metal carbonates such as calcium carbonate, and the like.
Alkali metal bicarbonates such as sodium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal C ₁ -C ₆ alkoxides such as potassium t-butoxide Such as, but not limited to, thallium (I) hydroxide and tri (C ₁ -C ₄ alkyl) amines such as triethylamine and mixtures thereof. Suitable bases include alkali metal carbonates, with potassium carbonate being more preferred.

In another preferred embodiment of the present invention, the compound of formula II
The 4-aryl-1-bromo-2-fluoro-2-butene of I is reacted with a palladium catalyst, a base and a boric acid of formula IV.

The boric acid of formula IV, the boric anhydride of formula V and the borate ester of formula VI can be prepared by reacting an aryl compound of formula VII with a tri (C ₁ -C ₄ alkyl) borate of formula VIII as shown in Scheme I. The borate of formula VI is formed and the borate of formula VI is spontaneously hydrolyzed with an aqueous acid to form another borate of formula IV
Of formula IV which can be combined with a compound of formula V to form boric anhydride of formula V
Of boric acid.

[0028]

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The starting compound of formula II, 4-aryl-2-fluoro-2-buten-1-ol, is prepared according to WO 94 / 06,7.
41 and GB 2,288,803.

In another preferred embodiment of the invention, the compound of formula II
4-aryl-2-fluoro-2-buten-1-ol with a brominating agent in a temperature range of about 50-130 ° C., and a 4-aryl-1-bromo-2-fluoro-2 of formula III -Butene with palladium catalyst, base and formula IV,
It is reacted with the compound of V or VI in a temperature range of about 50 to 130 ° C.

The preferred formula I which can be prepared by the process of the present invention
Wherein R is hydrogen and R ₁ is isopropyl, or R and R ₁ together with the carbon atom to which they are attached form a cyclopropyl group; , C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, be a C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-3 either phenyl optionally substituted by a combination; And A
r ₁ may optionally be substituted by any combination of 1 to 5 halogen, C _{1 to} C ₄ alkyl, C _{1 to} C ₄ haloalkyl, C _{1 to} C ₄ alkoxy or C _{1 to} C ₄ haloalkoxy groups. Good 3-phenoxyphenyl, optionally halogen, C
₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C _4, in any combination of one to five haloalkoxy group optionally substituted 3-biphenyl, optionally halogen , C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy group optionally substituted with 1 to 5 3-benzylphenyl Or as needed, halogen,
3-benzoylphenyl optionally substituted with any combination of 1 to 5 C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups There is something.

The method of the present invention preferably comprises R and R ₁
Is methyl, or R and R ₁ together with the carbon atom to which they are attached form a cyclopropyl group; Ar is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
Haloalkoxy groups are phenyl optionally substituted with any combination of 1 to 3; and Ar ₁ is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or used in the C ₁ -C ₄ production of pesticidal properties fluoroolefins of formula I wherein haloalkoxy group 1-5 either may 3-phenoxyphenyl which may be substituted with a combination.

To further understand the present invention, the following examples are provided primarily for purposes of more detailed description. The scope of the present invention should not be considered limited by this example, but encompasses all the objects defined in the claims.

[0034]

【Example】

Example 1 1- (p-chlorophenyl) -1- (3-bromo-2-
Production of (fluoropropenyl) cyclopropane, (Z)-

[0035]

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Under a nitrogen atmosphere, a solution of bromine (0.767 g, 4.8 mmol) in carbon tetrachloride at ice-water bath temperature was sequentially added to triphenylphosphine (1.2%) in carbon tetrachloride.
6 g, 4.8 mmol) and 3-solution in carbon tetrachloride.
[1- (p-chlorophenyl) -cyclopropyl] -2
-Fluoro-propen-1-ol, (Z)-(0.9
07 g, 4 mmol), heated, stirred under reflux for 70 minutes, cooled to room temperature and poured into petroleum ether. The resulting mixture was filtered and the filtrate was concentrated in vacuo to give a residue. The residue was dissolved in petroleum ether and passed through a layer of silica gel (eluted with hexane),
Oil was obtained. Flash chromatography of the oil on silica gel and a 3:20 methylene chloride / hexane solution produced the title product as a colorless oil (0.73 g, 63% yield) identified by NMR spectral analysis.

Example 2 1- (p-chlorophenyl) -1- [2-fluoro-3
-(4-Fluoro-3-phenoxyphenyl) propeni
R] cyclopropane, production of (Z)-

[0038]

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Under a nitrogen atmosphere, 1- (p-
Chlorophenyl) -1- (3-bromo-2-fluoropropenyl) cyclopropane, (Z)-(0.434 g,
1.5 mmol), 4-fluoro-3-phenoxybenzene boric acid (0.452 g, 1.95 mmol), potassium carbonate (1.86 g, 13.5 mmol) and bis (dibenzylideneacetone) palladium (0) [ Pd (db
a) ₂ , 4.3 mg, 0.075 mmol] was heated at 80 ° C. for 1 hour, cooled to room temperature, diluted with water and filtered through kieselguhr. The phases were separated and the aqueous phase was extracted with ethyl acetate. The organic phase and the ethyl acetate extract were combined, washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to give a residue. Flash chromatography of the residue using silica gel and a 3:20 methylene chloride / hexane solution gave the title product as N
A colorless oil identified by MR spectrum analysis (0.2
74 g, 63% yield).

As can be seen from Examples 1 and 2, 1-
(P-chlorophenyl) -1- [2-fluoro-3-
(4-Fluoro-3-phenoxyphenyl) propenyl] cyclopropane, (Z)-was obtained in a yield of 40% of 3-
[1- (p-chlorophenyl) -cyclopropyl] -2
-Fluoro-propen-1-ol, obtained from (Z)-. On the other hand, WO 94/06741
(P-chlorophenyl) -1- [2-fluoro-3-
(4-Fluoro-3-phenoxyphenyl) propenyl] cyclopropane, (Z)-was obtained in a yield of 20% of 3-
[1- (p-chlorophenyl) -cyclopropyl] -2
-Fluoro-propen-1-ol, which is disclosed as being obtained from (Z)-.

Example 3 1-Bromo-4- (p-chlorophenyl) -2-fluoro
Preparation of ro-methyl-2-pentene, (Z)-

[0042]

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Under a nitrogen atmosphere, triphenylphosphine (0.96 g, 4.2) in carbon tetrachloride at a temperature of -5 ° C.
5 mmol) of bromine (0.679) in carbon tetrachloride.
g, 4.25 mmol), heated,
Stir at room temperature for 45 minutes and add 4- (p-chlorophenyl) -2-fluoro-4-methyl-2-penten-1-ol, (Z)-(0.81 g, 3.54 mmol) in carbon tetrachloride. , Refluxed for 2 hours, cooled to room temperature,
And poured into petroleum ether. The resulting mixture was filtered through diatomaceous earth. The filtrate was washed successively with water, saturated sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. Flash chromatography of the oil using silica gel and a 1: 9 ethyl acetate / hexane solution gave the title product as an NMR.
Colorless oil identified by spectral analysis (0.736
g, 71% yield).

Example 4 4- (p-chlorophenyl) -2-fluoro-1- (4
-Fluoro-3-phenoxyphenyl) -methyl-2-
Production of pentene, (Z)-

[0045]

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Under a nitrogen atmosphere, 1-bromo-4- (p-chlorophenyl) -2-fluoro-4-methyl-2-pentene, (Z)-(320.8) in toluene (8 ml)
mg, 1.1 mmol), bis (dibenzylideneacetone) palladium (0) [Pd (dba) ₂ , 31.6 m
g, 0.055 mmol] of potassium carbonate (6
08 mg, 4.4 mmol), degassed, treated with 4-fluoro-3-phenoxybenzene boric acid (331.8 mg, 1.43 mmol) in ethanol (2 ml), refluxed for 45 minutes, and cooled to room temperature. And filtered through diatomaceous earth. The filtrate was diluted with ethyl acetate and the resulting solution was washed successively with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give a residue. Flash chromatography of the residue using silica gel and a 1: 9 ethyl acetate / hexane solution gave the title product as N
Colorless liquid identified by MR spectrum analysis (40
(1 mg, 91% yield).

As can be seen from the data in Examples 3 and 4, 4- (p-chlorophenyl) -2-fluoro-1- (4-fluoro-3-phenoxyphenyl) -methyl-2-pentene, (Z) -Is a 65% yield of 4-
(P-chlorophenyl) -fluoro-4-methyl-2-
Penten-1-ol, obtained from (Z)-. In contrast, UK Patent Application Publication No. 2,288,803
(P-chlorophenyl) -2-fluoro-1- (4-fluoro-3-phenoxyphenyl) -methyl-2-pentene, where (Z)-is 4- (p-chlorophenyl) -fluoro- with a yield of 37%. It is disclosed that it is obtained from 4-methyl-2-penten-1-ol, (Z)-.

Example 5 Preparation of 4-fluoro-3-phenoxybenzene boric acid

[0049]

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5-bromo-2- in tetrahydrofuran
A solution of fluorophenylphenyl ether (8.01 g, 3 mmol) in magnesium powder (0.0802 g, 3.0 mmol) in tetrahydrofuran at 50-55 ° C under nitrogen.
3 mmol), a mixture of iodine crystals and a few drops of 1,2-dibromoethane. After the addition was complete, the reaction mixture was stirred at 50-55 ° C for 70 minutes and cooled to room temperature. The cooled mixture was added over 20 minutes at a dry ice / acetone bath temperature to a solution of trimethyl borate (4.09 ml, 3.6 mmol) in diethyl ether. After the addition is complete, the mixture is stirred for 20 minutes at dry ice / acetone bath temperature and -10 minutes for 25 minutes.
Warm to ° C., dilute sequentially with acetic acid and water, stir at room temperature for 30 minutes and extract with ether. The organic extract was washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to give a residue. The mixture of the residue in water was heated on a steam bath for 30 minutes, cooled to room temperature and filtered to give a solid, which was washed with hexane and dried to give the title product as a colorless solid (5. 0.7 g, melting point 177-1
(80 ° C., yield 82%).

The main features and aspects of the present invention are as follows.

1. Structural formula I

[0053]

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Wherein R is hydrogen or C ₁ -C ₄ alkyl, R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ are the carbon atoms to which they are attached. Together form a cyclopropyl group; Ar
Is phenyl optionally substituted with any combination of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups. or optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C _4, in any combination of one to three haloalkoxy groups may be substituted Ar ₁ is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C 1-or 2-naphthyl;
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
Good phenoxyphenyl optionally substituted with any combination of 1 to 5 haloalkoxy group, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ ~
C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5
Any combination may biphenyl optionally substituted with the number, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5 Benzylphenyl optionally substituted with any combination of the above, or optionally halogen,
Benzoylphenyl optionally substituted with any combination of 1 to 5 C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups; And the stereostructure of the groups ArCRR ₁ — and —CH ₂ Ar _{1 to} the double bond is predominantly trans to each other in preparing a fluoroolefin compound of structural formula II

[0055]

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Wherein Ar, R and R ₁ are as defined above, and a 4-aryl-2-fluoro-2-buten-1-ol compound having the formula

[0057]

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Wherein Ar, R and R ₁ are as described above to produce a 4-aryl-1-bromo-2-fluoro-2-butene compound having the formula: Base and boric acid having structural formula IV, boric anhydride having structural formula V or boric ester having structural formula VI

[0059]

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Wherein R ₂ is C ₁ -C ₄ alkyl and Ar ₁ is as described above, wherein the reaction is with a fluorinated olefin compound having structural formula I.

[0061] 2. The method of claim 1, wherein the brominating agent is a bromine / triphenylphosphine complex.

3. The palladium catalyst is bis (dibenzylideneacetone) palladium (0), tetrakis (triphenylphosphine) palladium (0), bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, dichloride [ 1,4-bis (diphenylphosphine) butane] palladium (II),
[1,1'-bis (diphenylphosphino) ferrocene diacetate] selected from the group consisting of palladium (II), palladium (II) acetate, palladium (II) chloride and palladium on activated carbon and mixtures thereof; Metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal C ₁ -C ₆ alkoxide, thallium carbonate (I), thallium (I) C ₁ -C ₆ alkoxide, thallium hydroxide (I) and tri (C ₁ -C ₄ alkyl) is selected from amines and the group consisting of mixtures thereof, the method according to claim 1.

4. The method of claim 3 wherein the palladium catalyst is bis (dibenzylideneacetone) palladium (0) and the base is an alkali metal carbonate.

5. The method of claim 1 comprising reacting a compound of Formula III with boric acid.

6. Performing the first reaction step in a first solvent selected from the group consisting of aromatic hydrocarbons, halogenated aromatic hydrocarbons, carboxamides, ethers and halogenated hydrocarbons and mixtures thereof; reaction step an aromatic hydrocarbon, halogenated aromatic hydrocarbon, a carboxylic acid amide, glycol, C ₁ -C ₄ alcohols, ketones and ethers and mixtures thereof, and a second selected from the mixture the group consisting of water 2. The method according to 1 above, which is performed in a solvent.

7. The method of claim 6, wherein the first solvent is a halogenated hydrocarbon and the second solvent is toluene or a toluene / ethanol mixture.

8. The compound of formula II is combined with a brominating agent in about 50-1.
The reaction is carried out at a temperature of 30 ° C. and the compound of formula III is reacted with a palladium catalyst, a base and a compound of formula IV, V or VI for about 5 minutes.
The method according to the above 1, wherein the reaction is carried out at a temperature of 0 to 130 ° C.

9. Structural formula I

[0069]

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Wherein R is hydrogen or C ₁ -C ₄ alkyl, R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ are the carbon atoms to which they are attached. Together form a cyclopropyl group; Ar
Is phenyl optionally substituted with any combination of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups. or optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C _4, in any combination of one to three haloalkoxy groups may be substituted Ar ₁ is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C 1-or 2-naphthyl;
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
Good phenoxyphenyl optionally substituted with any combination of 1 to 5 haloalkoxy group, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ ~
C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5
Any combination may biphenyl optionally substituted with the number, optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5 Benzylphenyl optionally substituted with any combination of the above, or optionally halogen,
Benzoylphenyl optionally substituted with any combination of 1 to 5 C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups; And the configuration of the groups ArCRR ₁ — and —CH ₂ Ar _{1 to} the double bond is predominantly trans to produce a fluoroolefin compound of structural formula III

[0071]

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Wherein Ar, R and R ₁ are as described above, wherein the 4-aryl-1-bromo-2-fluoro-2-butene compound is present at a temperature of about 50 to 130 ° C. in the presence of a solvent. Under about 0.001 to 0.1 molar equivalents of a palladium catalyst, at least about 2 molar equivalents of a base and boric acid having structural formula IV, boric anhydride having structural formula V or boric acid ester having structural formula VI

[0073]

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Wherein R ₂ is C ₁ -C ₄ alkyl;
And a method for producing a fluoroolefin compound having the structural formula I, which comprises reacting Ar ₁ with the above.

10. The palladium catalyst is bis (dibenzylideneacetone) palladium (0), tetrakis (triphenylphosphine) palladium (0), bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, dichloride [ 1,4-bis (diphenylphosphine) butane] palladium (I
I), [1,1'-bis (diphenylphosphino) ferrocene] diacetate, selected from the group consisting of palladium (II), palladium (II) acetate, palladium (II) chloride and palladium on activated carbon and mixtures thereof; and When the base is an alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal C ₁ -C ₆ alkoxide, thallium carbonate (I), thallium (I ) C ₁ -C ₆ alkoxide, thallium hydroxide (I) and tri (C ₁ -C ₄ alkyl) is selected from amines and the group consisting of mixtures thereof,
10. The method according to 9 above.

11. The method of claim 10 wherein the palladium catalyst is bis (dibenzylideneacetone) palladium (0) and the base is an alkali metal carbonate.

12. 9. The solvent according to 9 above, wherein the solvent is selected from the group consisting of aromatic hydrocarbons, halogenated aromatic hydrocarbons, carboxylic acid amides, glycols, C ₁ -C ₄ alcohols, ketones and ethers, and mixtures thereof and mixtures with water. The described method.

13. Structural formula

[0079]

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[0080] In the formula, R is hydrogen or C ₁ -C ₄ alkyl, or R and R ₁ together with the carbon atom to which ones they are attached form a cyclopropyl group; R ₁
Is a C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ together with the carbon atom to which they are attached form a cyclopropyl group; Ar is optionally halogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ haloalkyl, C ₁
-C ₄ alkoxy or C ₁ -C ₄ haloalkoxy group 1
Phenyl optionally substituted with any combination of the three, or optionally halogen, C ₁ -C ₄ alkyl, C ₁
-C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C
₄ haloalkoxy groups are 1- or 2-naphthyl optionally substituted with any combination of 1 to 3 groups;
And the group ArCRR ₁ for the double bond
- and the compound three-dimensional structure of -CH ₂ Br is predominantly mutually trans.

14.1- (p-chlorophenyl) -1-
(3-bromo-2-fluoropropenyl) cyclopropane, (Z)-; and 1-bromo-4- (p-chlorophenyl) -2-fluoro-4-methyl-2-pentene;
The compound according to the above 13, which is selected from the group consisting of (Z)-.

15. Structural formula II

[0083]

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Wherein R, R ₁ and Ar are as described in 13 above,
The 2-buten-1-ol compound is dissolved in a solvent at about 50 to 1
Reacting at a temperature of 30 ° C. with a brominating agent selected from the group consisting of bromine-triphenylphosphine complex, phosphorus tribromide, thionyl bromide, HBr and mixtures thereof,
14. A method for producing the compound according to 13 above.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07C 41/30 7419-4H C07C 41/30 43/29 7419-4H 43/29 A 7419-4H Z // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yurin Hu 08536 Planesboro Hampshire Drive, New Jersey, United States 54 (72) Inventor David Allen Hunt, 18940 Nitown Water Lily, Pennsylvania, United States Way 9

Claims (4)

[Claims] 1. Structural formula I Wherein R is hydrogen or C ₁ -C ₄ alkyl, R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ together with the carbon atom to which they are attached Te form a cyclopropyl group; Ar is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ ~
C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-3
Optionally substituted with any combination of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl,
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
1- or 2-naphthyl optionally substituted with any combination of 1 to 3 haloalkoxy groups;
r ₁ may optionally be substituted with any combination of 1 to 5 halogen, C _{1 to} C ₄ alkyl, C _{1 to} C ₄ haloalkyl, C _{1 to} C ₄ alkoxy or C _{1 to} C ₄ haloalkoxy groups. Good phenoxyphenyl, optionally halogen, C _1-
C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5 either good biphenyl optionally substituted with a combination, optionally halogen, C ₁ ~ Benzylphenyl optionally substituted with any combination of 1 to 5 C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups; _{1 to} C ₄
Benzoylphenyl which may be substituted with any combination of 1 to 5 alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups. And the group Ar for the double bond
In producing a fluoroolefin compound in which CRR ₁ — and —CH ₂ Ar ₁ are mainly trans to each other, the structural formula II is used. Wherein Ar, R and R ₁ are as defined above, and reacting a 4-aryl-2-fluoro-2-buten-1-ol compound having a brominating agent with a brominating agent to form a compound of formula III Wherein Ar, R and R ₁ are as described above, to produce a 4-aryl-1-bromo-2-fluoro-2-butene compound having the formula: Boric acid having the formula IV, boric anhydride having the formula V or boric ester having the formula VI Wherein R ₂ is C ₁ -C ₄ alkyl and Ar ₁ is as described above, comprising reacting with structural formula I
A method for producing a fluoroolefin compound having: 2. Structural formula I Wherein R is hydrogen or C ₁ -C ₄ alkyl, R ₁ is C ₁ -C ₄ alkyl or cyclopropyl, or R and R ₁ together with the carbon atom to which they are attached Te form a cyclopropyl group; Ar is optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ ~
C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-3
Optionally substituted with any combination of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl,
C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄
1- or 2-naphthyl optionally substituted with any combination of 1 to 3 haloalkoxy groups;
r ₁ may optionally be substituted with any combination of 1 to 5 halogen, C _{1 to} C ₄ alkyl, C _{1 to} C ₄ haloalkyl, C _{1 to} C ₄ alkoxy or C _{1 to} C ₄ haloalkoxy groups. Good phenoxyphenyl, optionally halogen, C _1-
C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-5 either good biphenyl optionally substituted with a combination, optionally halogen, C ₁ ~ Benzylphenyl optionally substituted with any combination of 1 to 5 C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups; _{1 to} C ₄
Benzoylphenyl which may be substituted with any combination of 1 to 5 alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups. And the group Ar for the double bond
In preparing a fluoroolefin compound in which CRR ₁ — and —CH ₂ Ar ₁ are mainly trans to each other, the structural formula III is used. Wherein Ar, R and R ₁ are as described above, wherein the 4-aryl-1-bromo-2-fluoro-2-butene compound is reacted at a temperature of about 50-130 ° C. in the presence of a solvent at about 50-130 ° C. 0.001 to 0.1 molar equivalents of palladium catalyst, at least about 2 molar equivalents of base and boric acid having structural formula IV, boric anhydride having structural formula V or boric acid ester having structural formula VI Wherein R ₂ is C ₁ -C ₄ alkyl and Ar ₁
Is a process for producing a fluoroolefin compound having the structural formula I, which comprises reacting with the above. 3. Structural formula embedded image Wherein R is hydrogen or C ₁ -C ₄ alkyl, or R and R ₁ together with the carbon atom to which they are attached form a cyclopropyl group; R ₁ is C ₁ -C 4 ₄ alkyl or cyclopropyl, or R and R
₁ together with the carbon atom to which they are attached form a cyclopropyl group; Ar is optionally halogen, C _1-
C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy groups 1-3 or a phenyl optionally substituted with a combination, or optionally halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, in C ₁ -C ₄ alkoxy or C ₁ -C _4, in any combination of one to three haloalkoxy groups optionally substituted 1- or 2-naphthyl Has the structure of
And the groups ArCRR ₁ -and -CH ₂ B for the double bond
Compounds in which the configuration of r is mainly trans. 4. Structural formula II Wherein R, R ₁ and Ar are as described in claim 3, wherein the 4-aryl-2-fluoro-2-buten-1-ol compound having a temperature of about 50 to 130 ° C. in a solvent. With a bromine-triphenylphosphine complex, phosphorus tribromide,
The method for producing a compound according to claim 3, comprising reacting with a brominating agent selected from the group consisting of thionyl bromide, HBr and a mixture thereof.